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 SM ISO690:2012GORINCHOY, Natalia, BALAN, Iolanta, GORBACHEV, Mikhail, ARSENE, Ion, POLINGER, Victor, DUKA, Gh., BERSUKER, Isaac. Pseudo Jahn-Teller Effect in Transition States of Redox Processes. Hershey: 2023, pp. 71-110. ISBN 978-166847200-2, 978-166847198-2DOI: 10.4018/978-1-6684-7198-2.ch004 |
| EXPORT metadate: Google Scholar Crossref CERIF DataCite Dublin Core |
| Fundamental and Biomedical Aspects of Redox Processes | ||||||
| 2023 / ISBN 978-166847200-2, 978-166847198-2 | ||||||
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| DOI:https://doi.org/10.4018/978-1-6684-7198-2.ch004 | ||||||
| Pag. 71-110 | ||||||
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The authors show that the instability of the transition (activated) states of chemical reactions are due to the vibronic coupling of the ground electronic state with the appropriate low-lying excited states, resulting in the pseudo Jahn-Teller effect (PJTE). In application to reactions relevant to environmental problems, the PJTE origin of their activation barrier is illustrated by several examples, including the proton transfer in deprotonated H3O2- and protonated H5O2+(H2O)4 water clusters and in a number of proton-bound dimers. The results can serve as a general parametrized analytical model of the potential energy profile in simulating proton transfer processes in such systems. It also includes modeling the polarizing effect of the solvent, serving as an additional stabilizing factor in intramolecular H-bonds. Similarly, it is shown that the transition states of photochemical reactions are formed by the PJTE interaction of the relevant excited state with a higher in energy electronic state. Examples of electron transfer and charge transfer by coordination are also shown. |
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